Onderzoek aanwezigheid chemische stoffen in menselijk bloed Analyse van het gehalte chemische stoffen in de bloedstalen van drie Belgische ministers van Leefmilieu
©Greenpeace/E. de Mildt
December 2004
Determination of chemicals in human blood Report on chemical content in blood samples collected from three Belgian environment ministers Dr Fawaz Al Bitar – December 2004
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Onderzoek aanwezigheid chemische stoffen in menselijk bloed Analyse van het gehalte chemische stoffen in de bloedstalen van drie Belgische ministers van Leefmilieu Met dit onderzoek wil Greenpeace nagaan in welke mate in menselijk bloed gevaarlijke chemische stoffen voorkomen, die voordien zijn aangetroffen in het huisstof. Daartoe hebben we het bloed laten analyseren van drie Belgische ministers van Leefmilieu en van een directeur van Greenpeace. Dit onderzoek sluit aan bij een analyse op grotere schaal van het bloed van 91 Nederlanders.
Context Recent onderzoek van Greenpeace in verschillende Europese landen heeft een algemene chemische vervuiling vastgesteld van het huisstof. En dat in de woningen waar wij 90% van onze tijd doorbrengen. In België werden stalen van stof verzameld in 69 verschillende woningen, waaronder ook de woon- of werkplaats van 11 Belgische politici en verschillende kantoren van het Europees Parlement in Brussel. De resultaten toonden duidelijk aan dat alle onderzochte woningen en kantoren chemische stoffen bevatten die bio-accumuleerbaar (ze stapelen zich op in levend weefsel en in de voedselketen), weinig biologisch afbreekbaar (persistent) en mogelijk giftig zijn. Uit andere wetenschappelijke analyses blijkt dat deze gevaarlijke stoffen ook voorkomen in een ruime waaier van consumptiegoederen zoals sommige textielproducten, cosmetica en elektronische toestellen. Heel waarschijnlijk wordt de chemische vervuiling van onze woningen gedeeltelijk veroorzaakt door ons meubilair en andere veel gebruikte consumptiegoederen. De bio-accumuleerbaarheid en de geringe biologische afbreekbaarheid van de stoffen die zijn aangetroffen in de woningen en consumptiegoederen laten vermoeden dat het ook heel goed mogelijk is dat zij zich opstapelen in ons lichaam.
Deelnemers aan het onderzoek ♦ ♦ ♦ ♦
Mevrouw Evelyne Huytebroeck: Brussels minister van Leefmilieu De heer Kris Peeters: Vlaams minister van Leefmilieu De heer Benoit Lutgen: Waals minister van Leefmilieu De heer Wendel Trio: campagnedirecteur van Greenpeace België
Onderzochte stoffen - Gebromeerde vlamvertragers: vooral gebruikt in meubilair, elektrische en elektronische producten en in textielproducten. Mogelijke toxiciteit: invloed op het hormonale stelsel met ontwikkelingsstoornissen tot gevolg.
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- Ftalaten: vooral gebruikt in soepele kunststof, cosmetica en verf. Mogelijke toxiciteit: aantasting van de seksuele differentiatie, van de ontwikkeling van het voortplantingsstelsel, van de ontwikkeling en de functies van de lever, toegenomen risico van astma bij kinderen. - Organotinverbindingen: vooral gebruikt om PVC te stabiliseren en als schimmeldodend middel in tapijten en textiel. Mogelijke toxiciteit: verstoring van het immuunstelsel, van de ontwikkeling van het embryo en de testikels, aantasting van het enzymatisch systeem en neurotoxiciteit. - Alkylfenolen: vooral gebruikt in detergenten, cosmetica, shampoos en andere producten voor lichaamsverzorging. Mogelijke toxiciteit: verstoring van het hormonale stelsel, toxisch voor de voortplanting en beschadiging van het menselijk DNA.
Analyse van de resultaten Individuele opmerkingen ♦ Mevrouw Huytebroeck: elf gevaarlijke chemische stoffen werden aangetroffen in het bloed van mevrouw Huytebroeck. Zij behoren tot de volgende chemische groepen: gebromeerde vlamvertragers, ftalaten, organotinverbindingen en alkylfenolen. Op één uitzondering na waren al deze stoffen tijdens een voorafgaand onderzoek aangetroffen in het huisstof van het kantoor waarin mevrouw Huytebroeck enkele maanden geleden haar intrek heeft genomen. De hoogste concentraties aangetroffen in haar bloed, hadden betrekking op de ftalaten DEHP en DBP. Allebei kunnen ze ontwikkelingsstoornissen veroorzaken en staan ze in Europa geklasseerd als “toxisch voor de voortplanting”. De concentratie DBP in haar bloed behoorde tot de hoogste waarden die werden vastgesteld tijdens DBPanalyses, volgens dezelfde methode uitgevoerd op het bloed van 91 vrijwilligers in Nederland. Het bloed van mevrouw Huytebroeck was het enige Belgische staal dat aantoonbare concentraties bevatte van de organotinverbinding DBT, die storingen kan veroorzaken in de ontwikkeling van het immuunstelsel en het zenuwstelsel bij zoogdieren. Stoffen die mogelijk het endocriene stelsel kunnen verstoren, zoals nonylfenol en bisfenol-A, werden in haar bloed aangetroffen in een concentratie die overeenstemde met de hoogste meetresultaten bij de Nederlandse testgroep. ♦ De heer Peeters: veertien gevaarlijke chemische stoffen werden aangetroffen in het bloed van de heer Peeters. Zij behoren tot de volgende chemische groepen: gebromeerde vlamvertragers, ftalaten, organotinverbindingen en alkylfenolen. De meeste van deze stoffen waren al tijdens eerder onderzoek in ruime mate aangetroffen in het huisstof van de Belgische woningen. De hoogste vastgestelde concentraties hadden betrekking op de ftalaten DEHP, BBP en DBP. Deze zijn toxisch voor de voortplanting. De concentraties DBP en BBP in zijn bloed behoorden tot de hoogste waarden vastgesteld tijdens de analyse van deze stoffen, die volgens dezelfde methode uitgevoerd werden op het bloed van 91 vrijwilligers in Nederland. In het bloed van de heer Peeters werd ook het ftalaat DEP aangetroffen dat de ontwikkeling van het menselijk sperma kan verstoren. Zijn bloed was het enige Belgische staal dat aantoonbare concentraties bevatte van de organotinverbindingen MBT, MOT en DOT. Stoffen die het endocriene stelsel
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kunnen verstoren, zoals nonylfenol en bisfenol-A werden in het bloed van de heer Peeters aangetroffen in een concentratie die overeenstemde met de hoogste meetresultaten bij de Nederlandse testgroep. ♦ De heer Lutgen: zeven gevaarlijke chemische stoffen werden aangetroffen in het bloed van de heer Lutgen. Zij behoren tot de volgende chemische groepen: gebromeerde vlamvertragers, ftalaten en alkylfenolen. Op één uitzondering na waren al deze stoffen tijdens een voorgaand onderzoek aangetroffen in het huisstof van alle Belgische woningen. De hoogste concentraties in zijn bloed werden vastgesteld voor de ftalaten DEHP en DBP, en wel in een hogere concentratie dan de mediaan van de analyses die volgens dezelfde methode waren uitgevoerd op het bloed van 91 vrijwilligers in Nederland. In het bloed van de heer Lutgen werden ook andere ftalaten aangetroffen die bekend staan als gevaarlijk, zoals DEP. Stoffen die het endocriene stelsel kunnen verstoren, zoals nonylfenol en bisfenol-A werden in zijn bloed waargenomen in een concentratie die overeenstemde met de hoogste meetresultaten bij de Nederlandse testgroep. ♦ De heer Trio: tien gevaarlijke chemische stoffen werden aangetroffen in het bloed van de heer Trio. Zij behoren tot de volgende chemische groepen: gebromeerde vlamvertragers, ftalaten en alkylfenolen. Al deze stoffen waren al tijdens een eerder onderzoek aangetroffen in het huisstof van de Belgische woningen. De hoogste concentratie in zijn bloed werd vastgesteld voor het ftalaat DEHP, dat toxisch is voor de voortplanting. DEHP kan invloed hebben op de ontwikkeling van de testikels bij zoogdieren. In het bloed van de heer Trio werden ook nog andere stoffen aangetroffen die ontwikkelingsstoornissen veroorzaken: de ftalaten DBP en DEP. DEP is een stof die storingen kan veroorzaken in het menselijk sperma. De concentratie BDE-100, een gebromeerde vlamvertrager, behoorde tot de hoogste waarden vastgesteld in de analyses van BDE-100, die volgens dezelfde methode uitgevoerd werden op het bloed van 91 vrijwilligers in Nederland. Zijn bloed was het enige Belgische staal dat HBCD bevatte, een genetisch-toxische gebromeerde vlamvertrager. Stoffen die mogelijk het endocriene stelsel verstoren, zoals nonylfenol en bisfenol-A, werden in zijn bloed aangetroffen in een concentratie die overeenstemde met de hoogste meetresultaten bij de Nederlandse testgroep.
Algemene opmerkingen Tijdens dit onderzoek werden zestien soorten gevaarlijke chemische stoffen aangetroffen in de geanalyseerde bloedstalen. Al deze stoffen zijn eerder al aangetroffen in het huisstof van Belgische en Europese woningen en de meeste ervan zijn zelfs systematisch aanwezig in elke onderzochte woning. Bovendien zijn deze 16 chemische stoffen ook teruggevonden in een groot aantal consumptiegoederen: zuigflessen, speelgoed, verf, producten voor lichaamsverzorging, cosmetica, deodorants, pyjama's, T-shirts, regenjassen, sportschoenen, matrassen, gsm’s en ook computers. De resultaten van onze verschillende onderzoeken laten dus vermoeden dat de aanwezigheid van gevaarlijke chemische stoffen in onze consumptiegoederen leidt tot een systematische besmetting van onze woningen en tot een opstapeling van deze mogelijk giftige stoffen in ons lichaam. De concentraties die in deze studie zijn vastgesteld, stemmen overeen met de resultaten van het onderzoek dat volgens dezelfde methode is uitgevoerd bij 91 vrijwilligers in Nederland.
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Zijn de concentraties die in dit onderzoek zijn vastgesteld zorgwekkend? Alle vastgestelde concentraties zijn zorgwekkend, want er bestaat geen 'aanvaardbaar' niveau van concentratie voor de geanalyseerde stoffen in dit onderzoek. Aangezien deze stoffen moeizaam worden afgebroken en worden opgestapeld in menselijk weefsel en in de voedselketen, is het goed mogelijk dat de concentratie van deze stoffen in ons bloed de komende jaren nog zal toenemen. Verscheidene wetenschappelijke studies hebben inderdaad aangetoond dat de concentratie van sommige van deze stoffen in het menselijk weefsel de voorbije jaren al exponentieel is toegenomen. Zo is het bijzonder zorgwekkend dat er in het bloed van de deelnemers aan deze studie stoffen zijn aangetroffen die een verstorende werking kunnen hebben op het immuun- of het hormonale stelsel, of die schadelijk kunnen zijn voor de ontwikkeling en de voortplanting. Deze besmetting van het bloed van de Belgische ministers van Leefmilieu is, heel waarschijnlijk, een van de gevolgen van de toenemende chemische vervuiling in onze leefomgeving. Onlangs nog hebben verscheidene gerenommeerde wetenschappers samen de zogenaamde “Oproep van Parijs”1 gelanceerd. Daarin stelden zij dat deze chemische vervuiling mee de oorzaak vormt van het groeiend aantal slachtoffers van sommige ziekten zoals kanker, waarvan de frequentie de laatste jaren toeneemt.
Nood aan een doeltreffende wetgeving De aanwezigheid van gevaarlijke chemische stoffen in het huisstof van onze woningen en in ons lichaam lijkt erop te wijzen dat de controle op chemische stoffen niet doeltreffend verloopt. Het is dus van het grootste belang dat er een hervorming komt van de wetgeving met betrekking tot chemische stoffen. De Europese Unie werkt momenteel aan een nieuwe wetgeving die eenvormige regels moet opleggen voor de productie en de verkoop van chemische stoffen in Europa. Die wetgeving kreeg de naam REACH (“Registration, Evaluation, and Authorisation of Chemicals”- Registratie, beoordeling en vergunning van chemische stoffen). Volgens dat voorstel moeten chemische stoffen eerst geregistreerd worden en hun risico's beoordeeld, voor zij mogen verkocht worden. Onder druk van de industriële lobby is de reikwijdte van REACH al aanzienlijk afgezwakt. Om echt doeltreffend te zijn, moet REACH in elk geval het vervangingsprincipe bevatten. Dat houdt de systematische vervanging in van gevaarlijke chemische stoffen door veiliger alternatieven. Momenteel ligt REACH ter discussie en amendering voor in de Europese Raad en het Europees Parlement. De wet moet normaal in 2006 goedgekeurd worden. Nu duidelijk is aangetoond dat iedereen blootstaat aan de vervuiling met chemische stoffen, kunnen we alleen maar hopen dat de Belgische ministers van Leefmilieu hun verantwoordelijkheid zullen opnemen. Wij verwachten van hen dat zij ervoor zullen ijveren dat de Europese Raad instemt met een strengere REACH-wetgeving, waarin onder andere ook het vervangingsprincipe is opgenomen. Het is ook van kapitaal belang dat de Europese Parlementsleden rekening houden met deze studie en met het onderzoek van WWF, dat al eerder heeft aangetoond dat het bloed van verschillende Europese parlementsleden is besmet. Een reden te meer om te pleiten voor een strenger REACH. Alleen zo is het mogelijk om het gehalte te doen dalen aan gevaarlijke chemische stoffen in het bloed van de Europese burgers, en ernstige problemen voor de volksgezondheid te voorkomen.
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http://www.artac.info/
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Table of contents 1. Executive Summary................................................................................................... 7 2. Introduction ............................................................................................................... 8 2.1 Chemicals targeted for investigation.................................................................... 8 2.2 Dutch blood analysis ............................................................................................ 9 3. Materials and Method.............................................................................................. 10 3.1. Sample collection .............................................................................................. 10 3.2. Sample pre-treatment ........................................................................................ 11 3.3 Sample extraction............................................................................................... 11 3.4 Sample analysis .................................................................................................. 11 3.4.1 Bisphenol-A, alkylphenols and tetrabromo bisphenol-A ............................ 11 3.4.2 Brominated flame retardants and phthalates................................................ 11 3.4.3 Organotin compounds.................................................................................. 11 3.5 Identification, quantification and expression of results ..................................... 12 4 Results ...................................................................................................................... 13 4.1 General comments.............................................................................................. 13 4.2 Brominated flame retardants .............................................................................. 13 4.3 Phthalates ........................................................................................................... 14 4.4 Organotins .......................................................................................................... 15 4.5 Alkylphenols and Bisphenol-A .......................................................................... 15 5 Conclusions .............................................................................................................. 16 5.1 Individual results ................................................................................................ 16 5.2 General Findings ................................................................................................ 17 5.3 Regulation needed .............................................................................................. 17 6.QA/QC statement ..................................................................................................... 18 7. Acknowledgements ................................................................................................. 18 8. References ............................................................................................................... 23
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1. Executive Summary Blood samples from three Belgian environment ministers and the Campaign Director of Greenpeace Belgium were analysed and found to contain 16 of 33 hazardous chemicals that fall into four groups: brominated flame retardants, phthalates, organotins, and alkylphenols. These 16 chemicals have also been detected in a wide range of consumer goods - feeding bottles for infants, toys, paints, body care products, cosmetics, air fresheners, pyjamas, T-shirts, raincoats, sports shoes, mattresses, mobile phones, and computers – and in the dust of homes and offices in Belgium and other European countries. Consequently, the results of this study provide further evidence that the use of hazardous chemicals in consumer products contributes to the occurrence of these same chemicals as contaminants in the bodies of the population. The chemical contaminants in the blood of the four people in this study were present in the same general ranges as those measured in the blood of 91 volunteers from the Netherlands. However, concentrations of some chemicals were higher than the median values determined in the Dutch study. Since many of these are persistent, bioaccumulative chemicals that can damage the hormone, immune and development systems and can be toxic to reproduction, their presence at any concentration in human blood is of particular concern. Some have shown an exponential rise in concentrations in human tissue during the last 20 years. To reverse such trends and end human contamination, effective control of the production and use of chemicals must be enacted. The results of this study further corroborate the failure of current chemicals legislation to protect the population against widespread exposure to hazardous chemicals. The European Union is preparing plans for the most comprehensive system of chemicals regulation yet seen. A potentially far more effective system of chemicals regulation -Registration, Evaluation, and Authorisation of Chemicals (REACH) -- is currently being discussed by the European Parliament and Council and may become law by 2006.
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2. Introduction Innumerable scientific investigations have found hazardous chemicals in every environmental sector, including lake and marine sediments, remote polar regions and aquatic and terrestrial organisms, including humans. Several recent studies revealed that house dust samples collected all around Europe are contaminated with a variety of hazardous chemicals (Santillo et al., 2003a; Santillo et al., 2003b; Al Bitar, 2004). In Belgium, house dust was collected in 69 locations, including homes or offices of 11 Belgian politicians and several offices in the European Parliament in Brussels. Results indicated that every Belgian dust sample contained numerous chemicals that are persistent (they break down very slowly), bioaccumulative (they build up in fatty tissues of humans and other organisms), and toxic (Al Bitar, 2004). While the origins of these contaminants are not well documented, these hazardous chemicals most probably enter the dust as a result of losses from goods and furnishings present in the homes and offices where the samples were collected. Indeed, different investigations indicated that the same chemicals can be detected in a wide range of every-day consumer goods including textiles, cosmetics, shampoos and electrical goods (Peters, 2003a; Peters, 2003b; Pedersen and Hartmann, 2004). As a consequence of this contamination and of the intrinsic properties of these chemicals, some of them can be expected to accumulate in the bodies of the human population. The objective of the present study is to investigate the occurrence in the blood of three Belgian environment ministers and a Greenpeace Director of chemicals detected in Belgian house dust in a previous study. This analysis is also part of a broader study involving 91 people in the Netherlands (Peters, 2004). Some of the chemicals analysed have been demonstrated to damage the immune system, to have adverse effects on the reproductive system, and/or to cause a range of other health effects potentially associated with disruption of the endocrine system. 2.1 Chemicals targeted for investigation The chemicals analysed in this study have been chosen according to the following criteria: - their reported high volume use in common household furnishings and other products - their presence in house dust - their intrinsic hazardous properties (persistent, bioaccumulative and toxic) Therefore, the presence and concentrations of four main compound groups has been assessed: •
Brominated flame retardants are used to prevent or retard the spread of fire and may be applied to textiles or incorporated into plastics, foams and components of electrical goods. Suspected toxicity: interfere with hormone system and potentially affect growth and development
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Phthalate esters are used as softeners, heat-transfer fluids or solvents in PVC, wallpapers, furnishings, cables, cars, medical equipment, clothing, toys, ink, paint,
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adhesives, perfumes and cosmetics. Phthalates are considered as the most widespread man-made chemicals. Suspected toxicity: toxic to reproduction, impacts on the development and function of the liver, increased risk of asthma •
Organotin compounds are used as stabilisers, biocides, fungicides, antifouling compounds and/or catalysts in plastics (especially PVC), carpets and paints or applied to fruits and vegetables. Suspected toxicity: toxic to the immune system and affect embryo and testes development
•
Alkylphenols are used as non-ionic surfactants, emulsifiers, lubricants or antioxidants in the following kind of products: detergents, textiles, leather, paints, shampoos, cosmetics, some plastics and pesticides. Alkylphenols have recently been reported to be ubiquitous in German food. Suspected toxicity: hormone-disrupter, toxic to reproductive organs and harmful to human DNA
2.2 Dutch blood analysis In an earlier study, Greenpeace analysed blood samples from a representative group of Dutch people, for the presence of five groups of hazardous substances frequently used in consumer products. Ninety-one healthy volunteers participated, 48 males and 43 females. Their ages ranged from 19 to 78. Thirty-six of the 46 chemicals analysed were found in participants' blood, demonstrating that some chemicals found in consumer products are also found in human bodies (Peters, 2004). The brominated flame retardant BDE-153 was detected in 76 samples. The newer brominated compounds HBCD and TBBPA, which are increasingly widely used, were detected in 11 and 32 of the samples, respectively. The phthalates DEHP and DBP were detected in 84 and 68 samples, respectively. The limited occurrence and low levels of organotin compounds might be due to the restricted use of these chemicals in the Netherlands. Bisphenol-A was above detection limit in 36 of the samples. No correlation between any of the levels and age, sex, occupation or area of residence was observed. Only BDE-153 showed higher levels in males. The authors found man-made chemicals in all blood samples and concluded that the Dutch population is exposed to a variety of man-made chemicals (Meijer et al., 2004). A wide range of levels was detected for some compounds. The most likely explanation is differences in exposure.
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3. Materials and Method 3.1. Sample collection Blood samples were collected by doctors for Greenpeace Belgium using standard type BD-Vacutainer tubes. Each sample consisted of 6 tubes containing a total of approximately 60ml of blood. The following people participated in the investigation: ♦ Evelyne Huytebroeck: Environment Ministers for Brussels ♦ Kris Peeters: Environment Minister for Flanders ♦ Benoit Lutgen: Environment Minister for Wallonia ♦ Wendel Trio: Campaign Director of Greenpeace Belgium The samples were sent to the laboratory of TNO Environment, Energy and Process Innovation (TNO-MEP), Apeldoorn, the Netherlands, for analysis. The samples were kept cool during transport. The chemical parameters determined are listed below; including the abbreviations used in the text and accompanying tables and the method detection limits. Compound
Abbreviation Method detection limit
Brominated flame retardants 2,2',4-tribromo diphenylether 2,4,4'-tribromo diphenylether 2,2',4, 4- tetrabromo diphenylether 2,2',4,5'- tetrabromo diphenylether 2,2',3,4,4'-pentabromo diphenylether 2,2',4,4',5- pentabromo diphenylether 2,2',4,4',6- pentabromo diphenylether 2,2',4,4',5,5'-hexabromo diphenylether 2,2',4,4',5,6'- hexabromo diphenylether 2,2',3,4,4',5',6-heptabromo diphenylether decabromo diphenylether hexabromo cyclododecane tetrabromodisphenol-A
BDE 17 BDE 28 BDE 47 BDE 49 BDE 85 BDE 99 BDE 100 BDE 153 BDE 154 BDE 183
1 pg/g serum 1 pg/g serum 1 pg/g serum 1 pg/g serum 3 pg/g serum 3 pg/g serum 2 pg/g serum 1 pg/g serum 1 pg/g serum 2 pg/g serum
BDE 209 HBCD TBBPA
100 pg/g serum 80 pg/g serum 5 pg/g serum
DMP DEP DIBP DBP BBP DCHP DEHP DOP DINP DIDP
1 ng/g serum 1 ng/g serum 2 ng/g serum 2 ng/g serum 1 ng/g serum 1 ng/g serum 10 ng/g serum 1 ng/g serum 10 ng/g serum 10 ng/g serum
MBT DBT TBT TeBT MOT DOT TPT
0,1 ng/g blood 0,1 ng/g blood 0,1 ng/g blood 0.1 ng/g blood 0,2 ng/g blood 0,2 ng/g blood 0,4 ng/g blood
BPA NP OP
0,5 ng/g serum 0,5 ng/g serum 0,5 ng/g serum
Phthalates dimethyl phthalate diethyl phthalate d-iso-butyl phthalate di-n-butyl phthalate butylbenzyl phthalate dicyclohexyl phthalate di-(2-ethylhexyl)phthalate di-n-octyl phthalate di-iso-nonyl phthalate di-iso-decyl phthalate
Organotin compounds monobutyltin dibutyltin tributyltin tetrabutyltin monoctyltin dioctyltin triphenyltin
Phenols and alkylphenols bisphenol-A nonylphenol octylphenol
Table 1: Compound groups and specific compounds included in this study.
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3.2. Sample pre-treatment A sub-sample of the whole blood sample was collected for the organotin analysis. The remaining part of the whole blood sample was allowed to clot at room temperature for 20 min and centrifuged at 4,000 rpm for 15 min. The serum was transferred into PTFEcapped glass vials and stored at 4°C until further analysis. 3.3 Sample extraction All glassware used in the analyses was heated in an oven for 16 hours at 280°C prior to use. All solvents were distilled prior to use to achieve low blank results. The latter is especially important for the determination of the phthalates. The serum sample was weighed into a clean glass 60ml vial. Methanol, 0.1 M HCl and a set of internal standards (one or more for each group of chemicals) was added to the sample. The sample was extracted twice with a hexane-diethyl ether mixture and centrifuged after each extraction to separate the organic phase. The combined extracts were washed with a 1% KCl-solution and dried with anhydrous sodium sulphate. The extract was split into two equal parts, A and B. 3.4 Sample analysis 3.4.1 Bisphenol-A, alkylphenols and tetrabromo bisphenol-A Part A of the extract was concentrated to a small volume without further purification. Methanol was added to the extract and the extract was concentrated further to remove all hexane-diethyl ether residues. The methanol extract was used for the determination of BPA, NP, OP and TBBPA. The final extracts were analysed with liquid chromatography coupled with mass spectrometry (LC/MS) in the selected ion monitoring mode (SIM). 3.4.2 Brominated flame retardants and phthalates Part B of the extract was concentrated to a small volume. The extract was purified using a florisil clean-up procedure and separate fractions were collected containing the component groups. The purified extracts were concentrated to a small volume and an injection standard was added. The final extracts were analysed with gas chromatography coupled with mass spectrometry (GC/MS) in the selected ion monitoring mode (SIM). 3.4.3 Organotin compounds The whole blood sample was weighed into a 60ml vial and internal standards were added. After the addition of a sodium dithiocarbamate solution in ethanol, the sample was sonicated, left overnight, and sonicated once more. The residue was removed and an acetate buffer and a sodium tetraethylborate solution in ethanol were added. The mixture was extracted twice with hexane and the concentrated extract was purified using a silica clean-up procedure. The purified extract was concentrated and an injection standard was added. The final extracts were analysed with gas chromatography coupled with mass spectrometry (GC/MS) in the selected ion monitoring mode (SIM).
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3.5 Identification, quantification and expression of results The identification of analytes was based on correct retention times and qualifier ion ratios, compared to an external standard. The quantification was based on an external standard analysed together with the samples. The recovery of the added internal standards was used to determine the performance of the analysis, but not to correct the results of the target compounds with the exception of the organotin compounds. In the latter case the results were corrected for the recovery of the internal standard. The results in this report are expressed in pg/g serum (flame retardants) and ng/g serum (alkylphenols and phthalates). When reading the tables of this report please note that while results are rounded to the correct decimal number, they are not always rounded to the correct number of significant units. In general, no more than two significant numbers apply. In the tables, Belgian results are compared to Dutch blood analyses. Three percentiles (50th, 75th and 90th) are given to provide information about the shape of the distribution of these Dutch results. If the calculated percentile was smaller than the method detection limit, it was replaced by the method detection limit.
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4 Results 4.1 General comments The results of the Belgian samples are analysed in the following sections according to the chemical groups. In each table, the individual Belgian results are compared to the results from the Dutch analyses performed on 91 people, following the same methods as the present study (Peters, 2004). The Dutch mean value was not used for comparison as some abnormal values could disproportionately influence this mean. As some compounds were detected in only a few Dutch samples, the median value alone would not be appropriate for comparison since it would be below the detection limit. Thus, three percentiles including the 50th (median), 75th and 90th are given to provide information about the shape of the distribution of these Dutch results. The 50th, 75th and 90th percentiles are the concentration values that have, for the specified chemicals, 50%, 25% and 10% of higher concentrations, respectively. 4.2 Brominated flame retardants Thirteen types of brominated flame retardants were determined. Four were present at levels above the detection limit in the blood of Mr Trio; three in the blood of Mrs Huytebroeck and Mr Peeters; and one in the blood of Mr Lutgen (Table 2). BDE-153 was found in all samples. This is consistent with the widespread presence of this compound in the Dutch population (84%) (Peters, 2004), and with an examination carried out by WWF that reported an omnipresence (100%) of BDE-153 in the blood of some European politicians (Thomas, 2004). The BDE-153 concentration found in the blood of Mrs Huytebroeck is higher than the Dutch median. This compound has also been detected in some Belgian dust samples (Al Bitar, 2004) and in computers (Peters, 2003b). Both BDE-47 and BDE-100 that were also present in Belgian house dust were detected in the blood of Mrs Huytebroeck, Mr Peeters and Mr Trio. Their blood concentration in BDE-47 and BDE-100 were higher than the 75th percentile of the Dutch results, thus among the highest values measured in the Dutch population. HBCD that was found in computers (Peters, 2003b) was detected in the blood of Mr Trio as well as in 12% of the Dutch samples (Peters, 2004). pg/g 50th 75th 90th E. Huytebroeck K. Peeters B. Lutgen W. Trio serum percentile percentile percentile BDE-17 <1 <1 <1 <1 <1 <1 <1 BDE-28 <1 <1 <1 <1 <1 <1 <1 BDE-47 9.7 5.1 <1 5.8 <2 4.4 9.4 BDE-49 <1 <1 <1 <1 <1 <1 <1 BDE-85 <3 <3 <3 <3 <3 <3 <3 BDE-99 <3 <3 <3 <3 <3 1.8 6.8 BDE-100 3 2.9 <2 37 <2 <2 5.8 BDE-153 8.3 3.6 3.1 3.1 7.5 9.9 22 BDE-154 <1 <1 <1 <1 <1 <1 3.1 BDE-183 <2 <2 <2 <2 <2 <2 2.2 BDE-209 <100 <100 <100 <100 <150 <150 174 HBCD <80 <80 <80 112 <80 <80 114 TBBPA <5 <5 <5 <5 <50 85 170
Table 2: Brominated flame retardant content in Belgian blood samples.
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Individual results are compared to the 50th (median), 75th and 90th percentiles arising from blood analyses performed using the same method on 91 people in the Netherlands (Peters, 2004). The 50th, 75th and 90th percentiles are the concentration values that have 50%, 25% and 10% of higher concentrations, respectively. Abbreviations: BDE-brominated diphenylethers (tribromo- to decabromo-), HBCD-hexabromo cyclododecane, TBBA-tetrabromobisphenol-A.
4.3 Phthalates Six of the ten phthalates were detected in the blood of Mr Peeters; five in the blood of Mrs Huytebroeck; and four in the blood of Mr Lutgen and Mr Trio (Table 3). DEHP was present in all samples. The highest DEHP concentration, 206ng/g serum, was measured in the blood of Mr Lutgen, a concentration that is higher than the Dutch median. The pervasive presence of DEHP is consistent with the Dutch results (DEHP in 92% of the samples) and with the WWF studies (Peters, 2004; Thomas, 2004). The DBP concentrations in the blood of Mr Lutgen, Mrs Huytebroeck and Mr Peeters ranged from 41 to 89ng/g serum. This range of values is higher than the Dutch 75th percentile. In Mr Lutgen’s blood, the DBP concentration is even among the top 10% of concentrations in the Dutch study. These findings are not surprising since DEHP and DBP were also found in all the Belgian house dust samples (Al Bitar, 2004) and have been detected in consumer products such as body care products, cosmetics, pyjamas, air-fresheners, mobile phones, sports shoes, toys, mattresses or vinyl flooring (Peters, 2003a; Peters, 2003b; Pedersen and Hartmann, 2004). DEP and DIBP were also found in all Belgian blood samples. The blood of Mr Peeters also contained 2 other phthalates that were widely found in Belgian house dust (Al Bitar, 2004): DOP and BBP, which was found at a considerably higher concentration (42ng/g serum) than the 90th Dutch percentile. BBP was also detected in textiles, mobile phones, sports shoes, mattresses and vinyl flooring (Peters, 2003a; Peters, 2003b; Pedersen and Hartmann, 2004). ng/g E. Huytebroeck K. Peeters B. Lutgen W. Trio 50th 75th 90th serum percentile percentile percentile DMP <1 <1 <1 <1 <1 1.1 2.6 DEP 1 2.5 3.9 2.7 <2 <2 6.6 DIBP 9.7 19 16 7.7 <2 <2 52 DBP 59 41 89 6.8 8.1 19 63 BBP 1 42 <1 <1 <1 1.5 2.2 DCHP <1 <1 <1 <1 <1 <1 <1 DEHP 148 64 206 11 151 550 1680 DOP <1 1 <1 <1 <1 <1 <1 DINP <10 <10 <10 <10 <10 <10 <10 DIDP <10 <10 <10 <10 <10 <10 <10
Table 3: Phthalate content in Belgian blood samples.
Individual results are compared to the 50th (median), 75th and 90th percentiles arising from blood analyses performed, following the same method, on 91 people in the Netherlands (Peters, 2004). The 50th, 75th and 90th percentiles are the concentration values that have 50%, 25% and 10% of higher concentrations, respectively. Abbreviations: DMP- dimethyl phthalate, DEP- diethyl phthalate, DIBP- di-iso-butyl phthalate, DBP- din-butyl phthalate, BBP- butylbenzyl phthalate, DCHP- dicyclohexyl phthalate, DEHP- di-(2-ethylhexyl) phthalate, DOP- di-n-octyl phthalate, DINP- di-iso-nonyl phthalate, DIDP- di-iso-decyl phthalate
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4.4 Organotins Seven organotin compounds were tested. Three were detected in the blood of Mr Peeters and one in the blood of Mrs Huytebroeck (Table 4). The measured concentrations are roughly in the range of those found in the Dutch blood with DOT and MOT concentrations in the blood of Mr Peeters that are higher than the Dutch 90th percentile (Peters, 2004). The MBT, MOT and DOT found in the blood of Mr Peeters and the DBT found in the blood of Mrs Huytebroeck were also detected in each Belgian house dust sample (Al Bitar, 2004). These chemicals have been found in sports shoes, mattresses, T-shirt, pyjamas or raincoats (Peters, 2003a; Peters, 2003b; Pedersen and Hartmann, 2004). ng/g E. Huytebroeck K. Peeters B. Lutgen W. Trio 50th 75th 90th percentile percentile percentile blood MBT <0.1 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 DBT 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 TBT <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 TeBT <0.1 <0.1 <0.1 <0.1 / / / MOT <0.2 0.2 <0.2 <0.2 <0.1 <0.1 0.1 DOT <0.2 1 <0.2 <0.2 <0.1 <0.1 0.4 TPT <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 <0.4
Table 4: Organotin content in Belgian blood samples.
Individual results are compared to the 50th (median), 75th and 90th percentiles arising from blood analyses performed, following the same method, on 91 people in the Netherlands (Peters, 2004). The 50th, 75th and 90th percentiles are the concentration values that have 50%, 25% and 10% of higher concentrations, respectively. Abbreviations: MBT-monobutyltin, DBT-dibutyltin, TBT-tributyltin, TeBT-tetrabutyltin, MOTmonooctyltin, DOT-dioctyltin, TPT-triphenyltin
4.5 Alkylphenols and Bisphenol-A Three phenol compounds were investigated. Two were detected in the blood of Mrs Huytebroeck, Mr Peeters, Mr Lutgen and Mr Trio: BPA and NP (Table 5). The Belgian values were similar to the highest Dutch concentrations. Each BPA and NP concentration was higher than the Dutch 75th percentile. Both BPA and NP were found in all Belgian house dust samples (Al Bitar, 2004). BPA was detected in feeding bottles while NP was found in toys, pyjamas, sports shoes, mattresses, paints and vinyl flooring (Peters, 2003a; Peters, 2003b). ng/g E. Huytebroeck K. Peeters B. Lutgen W. Trio 50th 75th 90th serum percentile percentile percentile BPA 1.3 1.4 1.8 1.4 <0.5 1.1 2.5 OP <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 NP 1.1 2.3 1.3 3 <0.5 <0.5 1.2
Table 5: Alkylphenol and Bisphenol-A content in Belgian blood samples.
Individual results are compared to the 50th (median), 75th and 90th percentiles arising from blood tests performed, using the same method, on 91 people in the Netherlands (Peters, 2004). The 50th, 75th and 90th percentiles are the concentration values that have 50%, 25% and 10% of higher concentrations, respectively. Abbreviations: BPA-bisphenol-A, OP-octyphenol, NP-nonylphenol
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5 Conclusions 5.1 Individual results ♦ Mrs Huytebroeck carried eleven hazardous chemicals belonging to the following chemical groups in her blood: brominated flame retardants, phthalates, organotins and alkylphenols (Figure 1). All these chemicals but one had also been detected in the dust of her ministry in a previous investigation (Al Bitar, 2004). The highest concentrations in her blood were found for the phthalates DEHP and DBP, which are known developmental toxins, classified in Europe as “toxic to reproduction”. When compared to the Dutch blood investigation performed on 91 people, her DBP concentration was considerably higher than the 75th percentile, and so fell near the highest Dutch values. Mrs Huytebroeck was the only participant who carried detectable concentrations of the organotin DBT, in her blood. DBT is toxic to the developing immune and nervous system in mammals (Kergosien and Rice, 1998). Her blood also contained recognised and suspected endocrine disruptors such as nonylphenol and bisphenol-A at concentrations similar to the highest Dutch values. ♦ Mr Peeters carried fourteen hazardous chemicals belonging to the following chemical groups in his blood: brominated flame retardants, phthalates, organotins and alkylphenols (Figure 2). Most of these chemicals were widely detected in the Belgian house dust samples (Al Bitar, 2004). The highest concentrations in his blood were found for the phthalates DEHP, BBP and DBP, which are toxic to reproduction. Concentrations of DBP and BBP in his blood were considerably higher than the 75th percentile of the Dutch study and so were similar to the highest Dutch values. Another phthalate, DEP, which can affect the development of human sperm, was also present in Mr Peeters’ blood. His blood was the only Belgian sample to contain the organotins MBT, MOT and DOT. Recognised and suspected endocrine disruptors such as the nonylphenol and the bisphenol-A were also found in the blood of Mr Peeters, at concentrations higher than the Dutch 75th percentile. ♦ Mr Lutgen was found to carry seven hazardous chemicals belonging to the following chemical groups in his blood: brominated flame retardants, phthalates and alkylphenols (Figure 3). All but one of these chemicals were detected in all the Belgian house dust samples (Al Bitar, 2004). The chemicals present in the highest levels in his blood were the phthalates DEHP and DBP, which occurred at concentrations higher than the median concentrations in the Dutch study. Other hazardous phthalates such as DEP were also present in Mr Lutgen’s blood. Recognised and suspected endocrine disruptors such as nonylphenol and the bisphenol-A were also found in his blood, at concentrations higher than the Dutch 75th percentile. ♦ Mr Trio carried ten hazardous chemicals belonging to the following chemical groups in his blood: brominated flame retardants, phthalates and alkylphenols (Figure 4). All these chemicals have been found in Belgian house dust samples (Al Bitar, 2004). The highest concentration in his blood was found for the phthalate DEHP, which is toxic to reproduction. DEHP can interfere with testes development in mammals (Park et al., 2002). Other developmental toxins found in Mr Trio’s blood include the phthalates DBP and DEP. DEP can affect the human sperm development. The concentration in the brominated flame retardant BDE-100 in his
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blood was considerably higher than the 90th percentile arising from blood analyses performed on 91 people in the Netherlands and so was similar to the highest Dutch values. Mr Trio was the only participant whose blood contained the genotoxic brominated flame retardant HBCD. Recognised and suspected endocrine disruptors such as nonylphenol and bisphenol-A were also found in his blood at concentrations higher than the Dutch 75th percentile. 5.2 General Findings Sixteen hazardous chemicals were found in the blood of the four participants in this study. All of these chemicals were detected in the dust of Belgian and European houses and offices, with most of them occurring in every dust sample (Santillo et al., 2003a; Santillo et al., 2003b; Al Bitar, 2004). Moreover, these 16 chemicals have also been detected in a wide range of consumer goods: feeding bottles, toys, paints, body care products, cosmetics, air fresheners, pyjamas, T-shirts, raincoats, sports shoes, mattresses, mobile phones and computers (Peters, 2003a; Peters, 2003b; Pedersen and Hartmann, 2004). Consequently, the results presented here provide strong evidence that the ongoing use of hazardous chemicals in consumer products is associated with the occurrence of some of these chemicals in the bodies of the general population. Although further study is needed regarding the ways in which people are exposed to these compounds, it is very likely that exposure occurs through inhalation, ingestion or direct skin contact with contaminated dust and consumer products. The chemical concentrations found in this study are in the general range of those found in the blood of 91 volunteers from the Netherlands (Peters, 2004). These two studies have been performed according to the same protocol. All the detected concentrations are of concern given the intrinsic properties of the chemicals analysed, some of which have shown an exponential rise in concentrations in the tissues of the general population over the last 20 years (Meironyte et al., 1999). As these chemicals can damage the hormone, immune or development systems or are toxic to reproduction, their presence in human blood is, at any concentration, of particular concern. This was also recently stressed by scientists and Nobel prize-winners, who recognised that the development of numerous current diseases can be a result of this chemical contamination, and that the health of adults, children and future generations is under serious threat (The “Paris Appeal”). 5.3 Regulation needed The only way to end human contamination to hazardous chemicals is to adopt strong legislation that regulates the production and use of chemicals. The fact that the hazardous chemicals tested in this study are occurring in dust of ordinary homes and offices as well as in human bodies is a clear indication that current legislation to control such chemicals has failed. The European Union is preparing plans for the most comprehensive system of chemicals regulation yet seen. Known as Registration, Evaluation, and Authorisation of Chemicals (REACH), the regulation is currently being discussed by the European Parliament and Council and may become law by 2006. Chemical industry representatives succeeded in getting the text for REACH dramatically watered down before the Commission launched its proposal, with the result that it currently largely ignores the substitution principle. This states that if there is a safer substitute for a hazardous chemical currently used in the manufacture of a product and if that substitute is available at reasonable cost, then the hazardous substance will no longer be permitted for that use and will be replaced by the safer alternative. This principle is essential to the effectiveness of the REACH system.
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The present study has shown that Belgian environment ministers have hazardous chemicals in their blood. It is to be hoped that they will take into consideration their own test results, as well as the chemical contamination of the general population, and exercise their responsibility in leading the European Council to adopt an effective REACH legislation. It is also to be hoped that this study, together with the WWF study showing the levels of hazardous chemicals in the blood of various Members of the European Parliament (Thomas, 2004), will convince the European Parliament of the urgency to incorporate the substitution principle into REACH. This is the only way to ensure that European citizens of the future will not have to live with blood contaminated by hazardous chemicals.
6.QA/QC statement TNO-MEP operates in compliance with the quality standard ISO 9001, certificate number 07246-2003-AQ-ROT-RvA. This examination was performed in accordance with that ISO-9001 accreditation.
7. Acknowledgements Greenpeace Belgium is especially very grateful to Dr Hercot, Dr Brasseur and Dr Cazes for the blood collection. Greenpeace Belgium also thanks Dr Pat Costner for her detailed review of this report and her fruitful comments and Dr David Santillo and Katharine Mill for their critical review.
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Brominated Flame Retardants
12
Phthalates
160 140
10
ng/g serum
pg/g serum
120 8 6 4
60
20 0
BDE BDE BDE BDE BDE BDE BDE- BDE- BDE- BDE- BDE- HBCD -17 -28 -47 -49 -85 -99 100 153 154 183 209 TBBPA
Organotins
0.12
DMP
DEP
DIBP
DBP
BBP
DCHP DEHP
DOP
DINP DIDP
Alkylphenols
1.35 1.30
ng/g serum
0.1
ng/g blood
80
40
2 0
100
0.08 0.06 0.04
1.25 1.20 1.15 1.10
0.02
1.05 1
0 MBT
DBT
TBT
MOT
DOT
MPT
DPT
BPA
TPT
Figure 1: Chemical content in the blood of Mrs Huytebroeck, Environment Minister for Brussels.
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OP
NP
Brominated Flame Retardants
6
60
4
ng/g serum
pg/g serum
5
3 2
50 40 30 20
1 0
10 0
BDE BDE BDE BDE BDE BDE BDE- BDE- BDE- BDE- BDE- HBCD -17 -28 -47 -49 -85 -99 100 153 154 183 209 TBBPA
DEP
DIBP
DBP
BBP DCHP DEHP DOP DINP DIDP
Alkylphenols 2.5
1
2
ng/g serum
0.8
ng/g blood
DMP
Organotins
1.2
0.6 0.4
1.5 1 0.5
0.2 0
Phthalates
70
MBT
DBT
TBT
MOT
DOT
MPT
DPT
0
TPT
BPA
Figure 2: Chemical content in the blood of Mr Peeters, Environment Minister for Flanders.
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OP
NP
3.5
Brominated Flame Retardants
3.0
200
2.5
ng/g serum
pg/g serum
Phthalates
250
2.0 1.5
150 100
1.0 50
0.5 0
0
BDE BDE BDE BDE BDE BDE BDE- BDE- BDE- BDE- BDE- HBCD TBBPA -17 -28 -47 -49 -85 -99 100 153 154 183 209
DMP
DEP
DIBP
Alkylphenols 2 1.8 1.6
ng/g serum
1.4 1.2 1 0.8 0.6 0.4 0.2 0 BPA
OP
NP
Figure 3: Chemical content in the blood of Mr Lutgen, Environment Minister for Wallonia.
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DBP
BBP
DCHP
DEHP DOP
DINP
DIDP
Brominated Flame Retardants
100
10
80
8
60 40 20 0
Phthalates
12
ng/g serum
pg/g serum
120
6 4 2 0
BDE BDE BDE BDE BDE BDE BDE- BDE- BDE- BDE- BDE- HBCD TBBPA -17 -28 -47 -49 -85 -99 100 153 154 183 209
DMP
DEP
DIBP
DBP
Alkylphenols
3.5 3
ng/g serum
2.5 2 1.5 1 0.5 0
BPA
OP
NP
Figure 4: Chemical content in the blood of Mr Trio, Campaign Director of Greenpeace Belgium.
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BBP
DCHP
DEHP DOP
DINP
DIDP
8. References Al Bitar, F. (2004) Hazardous chemicals in Belgian house dust. Greenpeace Belgium, March 2004: 55 pp. Kergosien, D.H. and Rice, C.D. (1998) Macrophage secretory function is enhanced by low doses of tributyltin-oxide (TBTO), but not tributyltin-chloride (TBTCl). Arch. Environ. Contam. Toxicol. 34: 223-228. Meijer, L., Peters, R.J.B., Sauer, P. (2004) Man-made chemicals in human blood. Levels of forty-six chemicals in a Dutch cohort. Groningen, November 2004: 18pp. Meironyte, D., Noren, K. & Bergman, Å. (1999) Analysis of polybrominated diphenyl ethers in Swedish human milk. A time-related trend study, 1972-1997. Journal of Toxicology and Environmental Health - Part A 58(6): 329-341 Park, J.D., Habeebu, S.S.M. and Klaassen, C.D. (2002) Testicular toxicity of di-(2ethylhexyl)phthalate in young Sprague-Dawley rats. Toxicology 171: 105-115 Pedersen, H., Hartmann, J. (2004) Toxic Childrenswear by Disney. Greenpeace Investigations, April 2004: 33pp. Peters, R.J.B (2003a) Hazardous Chemicals in Consumer Products. TNO report R 2003/370, September 2003. Peters, R.J.B (2003b) The determination of selected additives in consumer products. TNO report R 2004/002, December 2003. Peters, R.J.B (2004) Man-made chemicals in human blood. TNO report R 2004/493, November 2004. Santillo, D., Labunska, I., Davidson, H., Johnston, P., Strutt, M. & Knowles, O. (2003a) Consuming chemicals: hazardous chemicals in housedust as an indicator of chemical exposure in the home. Greenpeace Research Laboratories Technical Note 02/2003, May 2003: 71 pp. Santillo, D., Labunska, I., Fairley, M. & Johnston, P. (2003b) Consommation toxique: Les substances dangereuses dans les poussières du logement comme indicateurs de l’exposition chimique dans l’environnement domestique. Greenpeace Research Laboratories Technical Note 02/2003, October 2003: 84 pp. Thomas, G.O. (2004) Analysis of man-made chemicals in human blood samples from 17 European countries. WWF-UK, March 2004: 91 pp.
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